The objective of this work was to prepare series of reduced-charge materials from different parent Li-saturated dioctahedral smectites, to investigate the effects of temperature, chemical composition and charge location in smectites on the charge reduction and to characterize reduced-charge smectites (RCSs) using methylene blue (MB) adsorption. The layer charge decrease, induced by Li fixation, is correlated with the trends in the spectra of MB-RCS dispersions in the visible region (VIS) spectra. Distribution of the negative surface charge of the clay minerals controls the distance between the adsorbed MB cations and thus affects the formation of MB dimers and higher agglomerates. Because each form of MB (monomer, dimer, higher agglomerate, J-aggregates) absorbs light at a different wavelength, the VIS spectra of MB depend sensitively on the charge density at the clay surface. Both cation exchange capacity (CEC) values and spectra of MB-clay dispersions clearly detect extensive reduction of the layer-charge density in reduced-charge montmorillonites (RCMs) upon Li-thermal treatment. The extent of charge reduction depends on the temperature of the thermal treatment, as well as on the octahedral charge of the montmorillonite. Reduction of the layer charge proceeds to a much lesser extent for smectites with mainly tetrahedral charge and high Fe content (Fe-rich beidellite and ferruginous smectite). Both CEC data and MB spectra detect only a slight decrease of the layer charge density, which relates to the low octahedral charge of these minerals. Following heating at higher temperatures (120-160°C), slightly higher Li fixation is indicated by CEC values; however, no charge reduction is confirmed by MB spectra. Release of protons accompanying Li+ fixation in Fe-rich smectites heated at 180 or 200°C was detected in the spectra of MB-clay dispersions and confirmed by potentiometric titrations.

Clay mineral diagenesis in the Niigata basin is documented by mineralogical and chemical analysis of clay minerals from cuttings from the Shinkumoide SK-1D (SSK-1D) well which is characterized by alternating beds containing dioctahedral and trioctahedral smectite minerals with increasing depth. Dioctahedral smectite shows a progressive increase in illite interstratification with increasing depth. The transition of dioctahedral smectite to interstratified illite-smectite (I-S) is supported chemically by an increase in K and Al and a decrease in Si with increasing depth. In contrast, trioctahedral smectite (saponite) reacts to form a 1:1 interstratified chlorite-smectite (C-S) with increasing burial depth and temperature. Considering the geology and the occurrence of smectite, the SSK-1D smectites probably altered diagenetically from two different parent materials: dioctahedral smectite is derived from clastic sediments and transforms to interstratified illite-smectite, whereas trioctahedral smectite is derived from andesitic pyroclastic rocks and transforms to interstratified chlorite-smectite.

The C-S occurs at the same depth of ~3200 m as the conversion of randomly interstratified (R = 0) I-S to (R = 1) I-S. Furthermore, the depth is compatible with a Tmax temperature of 430-435°C, which indicates the starting temperature for oil generation from organic matter. The temperature of the conversion of (R = 0) I-S to (R = 1) I-S and the start of corrensite formation is estimated at 110-120°C based on the time-temperature model suggested by others. The clay-mineral diagenesis in the SSK-1D further suggests that I-S and C-S can act as geothermometers in clastic and pyroclastic sediments provided that the effect of time is considered.

Molecular dynamics computer simulations were used to study methanol molecules confined between the layers of 2:1 phyllosilicates. The model systems are based on natural Ca- and Na-rich montmorillonites. Data from the literature and determined by fitting the calculated layer spacing to experimental values were employed to obtain interactions between the charged 2:1 layers and the solvent molecules. The montmorillonite surface atoms were held rigid and the methyl group in the methanol molecule was represented by a soft Lennard-Jones sphere. Electrostatic interactions were determined by the Ewald sum method, whereas the van der Waals interactions were described by a Lennard-Jones potential. Comparison of our results with diffraction data indicates a good reproduction of the layer spacing. After the initial solvent layer forms, additional solvent layers form only after previous layers are complete. Each Ca2+ and Na+ ion in the monolayer has four and two methanol molecules, respectively, in the first solvation shell, whereas the solvation shell in the multilayer contains six and four methanol molecules, respectively. This agrees well with experimental data.

Infrared (IR) spectroscopy has a long and successful history as an analytical technique and is used extensively (McKelvy et al., 1996; Stuart, 1996). It is mainly a complementary method to X-ray diffraction (XRD) and other methods used to investigate clays and clay minerals. It is an economical, rapid and common technique because a spectrum can be obtained in a few minutes and the instruments are sufficiently inexpensive as to be available in many laboratories. An IR spectrum can serve as a fingerprint for mineral identification, but it can also give unique information about the mineral structure, including the family of minerals to which the specimen belongs and the degree of regularity within the structure, the nature of isomorphic substituents, the distinction of molecular water from constitutional hydroxyl, and the presence of both crystalline and non-crystalline impurities (Farmel, 1979).

The OH-stretching region in curve-fitted micro-Raman, photoacoustic and transmission IR spectra of St. Claire dickite was investigated. Polarized Raman spectra recorded from th. (001) an. (010) faces of the dickite crystal displayed six prominent OH bands. The relative intensities depend strongly on both the orientation of the crystallographic axes and the direction of the electric vector of the laser beam. Four out-of-plane vibrations, AA, Az, CA and Cz, at ~3710, 3706, 3654 and 3643 cm-1 respectively, predominate when the electric vector is perpendicular to the dickite plates. Two in-plane vibrations, Dz and DA at 3627 and 3623 cm-1, intensify when the electric vector is parallel to the plane. The relationship between band intensity and crystal orientation was interpreted in terms of longitudinal optic (LO) and transverse optic (TO) crystal vibration modes. These LO and TO crystal modes were also observed in curve-fitted photoacoustic and transmission IR spectra of coarse, non-oriented crystals of the dickite.

The alteration process of a subvolcanic rock with calcic plagioclase, pyroxene, and olivine as major components was investigated by X-ray diffraction (XRD) and analytical and transmission electron microscopy (TEM/AEM). Experimental interaction with 1 M NaOH solution led to the formation of dioctahedral beidellite to Fe-rich montmorillonite after 1 and 3 d of reaction. This range of smectite composition is similar to that from natural subvolcanic-derived soil formed from the same parent material. After 14 d of reaction, a berthierine-smectite (B-S) interstratified clay had partially replaced the smectite. Although, the presence of smectite interlayers prevented analysis of pure berthierine, berthierine-rich BS interstratifications have a composition similar to pure berthierine. After 40 d, the alteration process led to a 7-Å S interstratification whose composition falls between greenalite and lizardite. A series of amorphous materials were also found in the 14 and 40-d experiments. The most abundant of these is a Si-CaFe-rich material, whose chemical composition approaches that of the starting rock. In contrast, two other amorphous materials had a smectitic composition.

Nacrite and dickite are found in two localities in northern Taiwan. One, containing nacrite and dickite, is associated with a gold-enargite deposit as a vug-filling clay in the Chinkushih (CKS) mine district near the northern coast. The other is the occurrence of dickite in the interstices of a Miocene coarse-grained quartzose sandstone in the Nanshihchiao (NSC) area, near Taipei city. X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscope (SEM), and petrographic examinations were used to characterize the mineralogical features. Nacrite most often takes the unusual form of rhombic platelets, and dickite is commonly elongated in habit with the shapes possibly related to their origin. Based on geological evidence, we believe that both nacrite and dickite are of hydrothermal origin. In the CKS area, the formation of nacrite and dickite is related to the hypogene gold-enargite mineralization. In contrast, the transformation of dickite in the NSC area is due to the influence of the raised temperatures of sandstone formation, resulting from volcanic activity during the Kungkuan stage after the deposition of the sandstone.

The transformation of kaolinite to halloysite-7 Å was identified in the kaolin deposit of São Vicente de Pereira (SVP), using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Both the 02, 1̄ and 13̄, 13 reflections show changes in the XRD patterns along the kaolinite to halloysite-7 Å transition, and the FTIR spectra show changes corresponding to both OH− and Si-O-stretching bands and Al-O-Si-bending vibrations. The interlayer water content in the kaolinite structure increases during transition. The two-layer periodicity of well-ordered kaolinite and rolling up of kaolinite plates are observed using high-resolution transmission electron microscopy (HRTEM). Long and short tubes exhibit halloysite-7 Å. No structural Fe was found in the kaolinite samples. Analytical electron microscopy (AEM) indicates no substitution of Al3+ for Si4+. The Si/Al ratio shows values of ∼1 for the kaolinite and rolled kaolinite plates. The 27Al magic angle spinning neutron magnetic resonance (MAS-NMR) spectra display a resonance centered at ∼1 ppm, assigned to six-coordinated aluminum. The transformation of kaolinite to halloysite-7 Å is controlled by surface reaction.

Three ball clays (SP from England, TSMA from France and UK from the Ukraine) were characterized for their dry and wet colloidal properties. On the basis of X-ray diffraction and chemical analyses the clays were classified as kaolinite-rich clay, smectitic kaolinite-rich clay and illitic kaolinite-rich clay. The ζ (zeta) potential at the clay-water interface as a function of pH, in three different electrolytes, was investigated using an electroacoustic technique. Starting from measurements of dynamic mobility, the calculated ζ potential was found to be almost constant as a function of pH for the TSMA and UK clays, while it increased from −20 to −60 for the SP clay, when potassium nitrate was used as an electrolyte. The behavior of the three clays in calcium and magnesium nitrate was slightly different: SP showed a smaller increase in ζ potential, while a small deviation from the constant behavior of the UK clay was found. The results are explained in terms of the surrounding-ion atmosphere in light of the chemical-physical properties measured. Our results may well be of use to those involved in ceramic processing.

Thermal analysis involves a dynamic phenomenological approach to the study of materials by observing the response of these materials to a change in temperature. This approach differs fundamentally from static methods of analysis, such as structural or chemical analyses, which rely on direct observations of a basic property of material (e.g. crystal structure or chemical composition) at a well-defined set of conditions (e.g. temperature, pressure, humidity). Clay minerals are highly susceptible to significant compositional changes in response to subtle changes in conditions. For example, changes in the fugacity of water affect the stability of interlayer H2O in a clay mineral (see below). Therefore, care must be taken that all experimental conditions are known with accuracy and precision

The Madayi clay deposit consists of a thick sequence of residual white kaolinitic clay underlying the sedimentary Warkallai Formation, which includes gray carbonaceous kaolinitic clays, lignite, ferruginous kaolinitic clays, laterite and bauxite with ferricretes. The conditions of clay genesis and the economic significance of the major residual kaolin seam have been investigated. The raw clay and <2 μm fractions were subjected to X-ray diffraction (XRD), chemical analysis, differential thermal analysis (DTA), Fourier transform infrared (FTIR) spectroscopic and scanning electron microscopic (SEM) studies. The firing behavior of the <45 μm fraction of the major residual clay sequence (L), was investigated systematically to determine the potential industrial use of this kaolin.

Geochemical and morphological studies of different strata indicate the following conditions for clay formation. (1) intense lateritized weathering conditions for kaolinization of the residual white clay from parent quartzo-felspathic mica-gneiss. (2) reducing environment for the gray carbonaceous layers; an. (3) oxidizing environment for the uppermost hematite-rich ferruginous clay. Pyrite/marcasite enriched detrital gray carbonaceous clay shows two distinct environments for in situ kaolinite crystallization. (1) within plant fossils influenced by the high organic content and FeS2 leaching; and (2) precipitation from solution.

Incomplete kaolinization of white residual clay is evident from the presence of pyrophyllite, muscovite with lenticular cleavage void and a lower percentage of fines (<2 μm). The plant fossils from the uppermost portion of residual clay show pyrite mineralization. The Hinckley Index, FTIR and rare earth analysis point towards diverse geochemical environments of deposition and technological evaluation indicates its suitability for application in the ceramics industry.

Competitive adsorption between glyphosate and phosphate on goethite was evaluated. The influence of background electrolyte on the adsorption of glyphosate and phosphate was also investigated by using 0.01 M KCl, 0.1 M KCl and 0.01 M CaCl2 as background electrolytes. Experiments showed that phosphate displaced adsorbed glyphosate from goethite, whereas glyphosate did not displace phosphate. Results also showed that the background electrolyte had a strong effect on phosphate adsorption, but little effect on glyphosate adsorption. Thus, there are differences between the adsorption of glyphosate and phosphate. The study also showed that 0.01 M KCl caused dispersion of goethite, resulting in inefficient filtering, and that phosphate precipitated as calcium phosphates in 0.01 M CaCl2 background electrolyte solutions. The results suggest that 0.1 M KCl is a more suitable background electrolyte to determine competitive adsorption processes involving glyphosate and phosphate.

The cation exchange capacity (CEC) of fine-grained materials, and especially clay minerals, is a fundamental property of these materials, and can be determined routinely. A search of the recent literature illustrates the great interest of this property to researchers. For example, a search of the GeoRef database for references to “cation exchange capacity” for the years 1980 to 1999 yields 2559 citations.

The interface between the surfaces of clay minerals and other materials (aqueous solution, organic moieties, biomolecules, etc.) is of great importance to many geological, technological and biological processes. The examination of the structure and composition of mineral surfaces is advancing rapidly. However, the crystal structure of a mineral is only part of the information needed to understand the activity of the surface; we still do not fully understand the chemical and physical interactions at the surface or interface. One very powerful methodology for the study of surfaces and interfacial interactions is the determination of the thermodynamic properties of the surface. It became possible in the late 1980s to determine quantitatively the apolar and polar surface-tension components and parameters of liquids and solids (van Oss et al., 1988; van Oss, 1994), and the experimental techniques necessary for obtaining surface free-energy components of minerals, and particularly of colloid-sized minerals, are also a recent development (Costanzo eta!., 1990; van Oss et al., 1990, 1992; Giese et al., 1991).